Organic lead salt stabilizers for vinyl halide resins



butyrate, vinyl hexoate, vinyl acetobutyrate, vinyl Patented Dec. 7, i9 1 2,455,879

UNITED STATES PATENT orrlcs ORGANIC LEAD SALT STABILIZERS FOR VINYL HALIDE RESINS Moyer M. Safiord, Schenectady, N. Y., assignor to General Electric Company, a corporation of New York No Drawing. Application May 13, 1946, Serial No. 669,469

10 Claims. (01. 260-86) 1 r 2 The present invention relates to vinyl resins I have found that the compounds of the class and more particularly to vinyl resins stabilized represented by the general formula against the action of heat and light and deteri- H o oration of electrical properties. ll

Broadly, my invention relates to the heat and 5 t light stabilization of resinous compositions pro- HI duced by polymerizing compositions comprising a vinyl halide with or without other copolymerizo Pb able compounds. Among such compositions are a (1) the polyvinyl halides, such as, for example,

polyvinyl chloride (including the diiferent molec- I ular weight forms, e. g., gamma-polyvinyl chloride), polyvinyl bromide, etc.; (2) vinyl resins produced by the conjoint polymerization of a vinyl halide, e. g.,vinyl chloride, and a vinyl ester of a lower saturated aliphatic monocarboxylic acid, e. g., vinyl acetate (such vinyl chloride-vinyl acetate copolymers being available under the trade name of Vinylite resins wherein the vinyl chloride component is present in a preponderant amount), vinyl propionate, vinyl where R is an alkyl radical containing at least 15 3 and not more than 10 carbon atoms and R is an alkyl radical containing at least 1 and not more than 5 carbon atoms, are excellent heat and light stabilizers for vinyl halide resins. Illustrative examples of alkyl radicals represented by R are: propyl, butyl, hexyl, isobutyl, isoamyl, 2-ethylhexyl, decyl, etc.; illustrative examples of radicals represented by R are methyl, ethyl, propyl, butyl, isopropyl, amyl, etc. Preferably R is an alkyl radical containing 10 carbon atoms and R is a methyl group.

The chemical compounds employed as heat, light and electrical stabilizers for the vinyl resins may be prepared by various methods. One methed, as illustrating the preparation of the compound employed in the subsequent examples, comprises first preparing the n-decyl-substituted suecinic anhydride derivative having the formula chloroacetate, vinyl chloropropionate, etc.; it being obvious from the foregoing examples that the term lower saturated aliphatic monocar- 25 boxylic acid" embraces ones containing at most six carbon atoms; (3) vinyl resins produced by the conjoint polymerization of a vinyl halide and an acrylic compound, e. g., the copolymers of vinyl chloride with, for example, ethyl methac rylate, methyl methacrylate, benzyl or chlorobenzyl acrylate, methyl chloroacrylate, etc.;

(4) copolymers of a vinyl halide, e. g., vinyl chlo- H 0 ride, and a vinylidene halide, specifically vinyli- CwHu-- dene chloride; and (5) many other vinyl resin copolymers, such as the copolymers of threecomponent systems, for example, vinyl chloride,

H| --0 vinyl acetate and ethyl methacrylate, etc. As

will be understood by those skilled in the In the preparation of the n-decyl substituted other lnulti'c9mponent copolymers m be used 40 succinic anhydride derivative under discussion, the only requirement being that at least one of mdecane is caused to condense with maleic anhythe components is a vinyl halide. Further .methdride by t th d di l d in Binapfi-U. S. ads of preparation of the vinyl halide resins emt t 2,121,183, issued- June 21, 1938, which p y d h r and addltiona exampl s f vvinyl patent teaches that saturated aliphatic hydro-- halide copolymers which may be stabilized with carbons, such as propanerbutane', pentane, isothese lead salts may be found in. r mple. pentane, hexane,. heptane,octane,--etc.; may be DAl l P te 2, 7 ,753, issuedJune 19. 1 4 condensed with maleic anhydride. The n-decyland 2,299,740, issued October 27, 1942, both of substituted succinic anhydride thus formedis which are assigned to the same assignee as the then reacted with an amount ofmethyl alcohol present invention. sumcient to give. the haltesteroi the n-decy-lgeneral formula minutes on differential rolls, the front roll of which was heated with steam under a pressure oi H about 20 to 30 pounds per sq. in. The compound 0 H J JL after milling was then molded for about 5 min- 5 utes at a temperature 01 150 C. under a. pressure H: -OOH of 500 pounds per sq. in. The sample thereby obtained. which was very pale yellow in color, was divided into several equal par-ts. Each portion (See the method disclosed by Bone, Sudborough, s h at-aged at 150 C. for p riods of time va yg Spranknng Journal 1 t chemical society ing from 1 minute to 90 minutes, and the effect of of London, vol. 85, page 539.) This derivative is this heat-agin noted. As a control, another in turn heated with PhD at a temperature high sample of 60 parts polyvinyl chloride was comenough to eflect reaction between the ingredients P u d h 0 pa ts t i r syl phosp at itto yield the compound (or compounds) employed ting the stabilizer in this case. This sample was as stabilizers in my invention. A also pressed under the same conditions disclosed In order that those skilled in 'the art may better above and divided into equal portions which were understand how the present invention may be heat-aged for the same lengths or time and under practiced, the following examples are given by the same conditions asthose described above for way of illustration and not by way of limitation. the samples containing the stabilizer. The lol- The resin employed in Example 2 is a copolymer lowing tables show the results of these heat-aging of vinyl chloride and vinyl acetate, the vinyl chlotests. as well as the results of the electrical tests ride being present in the polymerizable mixture conducted at C. It was noted that upon reprior to copolymerization in an amount equal to moval of the stabilized and unstabillzed samples approximately 85% of the total weight of the from the mold, the latter sample was already bemonomers. 25 ginning to turn red, whereas the stabilized sample 1 an parts are try weight. was almost colorless.

Teens 1 Stabilized.

Aging grime D 1 P L0 Volume g g g- 023.2233? F3333; 5335 3 $335353...

5 58x10" Very pale yellow. Do. Do. Do. 3 00x10 Do. Light yellow. Do. a 75x10 Do.

Tessa H Unstabilieed Aging Time D 1, L0 Volume 1 can: F3228; 3153 73 33553...

3 12x10 Dark brown.

Do. Do. Do. iesxio Do. Very dark brown.

Do. 6.50Xl0 D0.

Parts Parts Polyvinyl chloride 53 Lead salt or the n-decyl-substituted succinic Besimus g? g acid methyl half ester mass cons y we g 0 per cen Tricresylphosphate (p1 as m er) vinyl chloride and 15 per cent vinyl acetate 63 i This compound has the structural formula:

v E 0 5 OnHzi-iS-E-G-OH; In '0-0 The above components were milled for about '10 v Lead salt of the n-decyl-substituted succinlc acid methyl half ester (same as used in Example 1) 2 Tricresyl phosphate (plasticizer) 35 The above ingredients were compounded on di f ferential rolls and pressed in the same manner as shown in Example 1. Samples of this compound. as well as samples compounded and pressed from the same ingredients from which the stabilizer (the lead salt) was omitted, were heat-aged and tested for their electrical properties in the manner ioliowed in, Example 1. The following tables r. show the results of these tests on the stabilized unstabilized samples:

Lead salt of monoethyl ester of n-decyl-substituted succinlc acid Tuna III Stabilized Dielectric Power Loss Physical C. Resistivity 1n ggfg Constant Factor Factor ohms/Cm? Appearance Light yellow.

Do. D0. D0. Light amber Do. Do.

TABLE IV Unstabilized Aging Time Dielectric Power Loss volume Physical Resistivity In si lifi l s y Constant Factor Factor mung/Cm Appearance Dark brown.

Do. Do. D 6. l2 0. 197 1. 230 Blacklsh brown. 6. 87 0. 255 1. 800 8. 50x10" D0. 6. 68 0. 258, l. 810 8. 23x10 D0.

From the foregoing examples it will 'be apparent that vinyl resins employing the lead stabilizers .disciosed previousl are able to maintain their light color despite the fact that they were heated at temperatures which caused the unstabilized materials todarken and decompose. Further more the electrical proper-ties of the stabilized products were constant over a relatively long ployed in the test, while the electrical properties of the unstabilized products, due to their decomposition, increased tosuch a magnitude as to make them undesirable for use as electrical insulation materials. Since vinyl resins are used extensive- 1y as electrical insulation materials, such a defect is quite serious.

Although in the above examples from about 3.2 to 3.5% stabilizer by weight, based on the amount of the vinyl resin. has been employed, I do not intend to be limited to such ranges. Thus, I may use from, for example, about 0.5 to 5% or stabilizer, by weight, based on the amount of the vinyl resin. Although amounts in excess of 10% may be employed, for economical reasons I prefer not to use larger amounts.

It will be understood, of course, by those skilled in the art that my invention is not limited to the stabilization of polymers or copolymers of a vinyl halide'with the particular lead salt disclosed in the foregoing examples. Instead of using the stabilizer disclosed above, I may employ other lead salts of the half ester alkyl-substituted succinate having less than 10 carbon atoms in the alkyl radical and more than 1 but less than 5 carbon atoms in the alcohol ester grouping, examples of which are:

Lead salt of monomethyl ester of octyl-substituted succinic acid Lead salt of monomethyl ester of amyl-substituted succinic acid Lead salt of monomethyl ester of isobutyl-substituted succinic acid Lead salt of monomethyl ester of propyl-substituted succinic acid Lead salt of monoethyl ester of octyl-substituted -succinic. acid period of timeat the elevated temperatures em- Lead salt of monoethyl ester of neopentyl-substituted succinic acid Lead salt of monoisopropylester of isobutyl-substituted succinic acid Lead salt oi monobutyl ester of n-decyl-substituted succinic acid The above compounds may be readily prepared by the method previously disclosed herein by using the corresponding alkanes in the preparation of the alkyl-substltuted succinic anhydride derivative, and thereafter eilecting reaction with the desired saturated aliphatic alcohol.

In the compounding of plastic compositions for various uses, there may be included any of the common solvents, plasticizers; e. g.,- dioctyl phthalate, dibutyl phthalate; etc., pigments and other modifying materials without detrimental effect upon the heat, light, and electrical stability afforded by these new stabilizers. Various means well known to the art'may be used for incorporating the stabilizers of this invention into the resinous compositions. Since the stabilizers used are high-boiling liquids, the resin, plasticizer and stabilizer may be dissolved in a mutual solvent and intimately mixed, followedby the evaporation of the solvent ifxthe composition'is not to be used as a varnish. Sheeting on differential rolls, as was used in the examples, may also be employed. It is important to obtain as intimate and complete a dispersion or solution of the stabilizer in the resinas is possible. The usual stabilizers; like Pb0-(litharge) which are solids, are diflicultto disperse. The compounds employed in the practice of this invention are soluble in the plasticizer and hence no difllculty is encountered in its dispersion. Therefore, a more efllcient utilization of a-g'iven weight of this stabilizer results;

The stabilized vinyl halide polymers and'copolymers of this invention may be used not only for compression, extrusion, and injection molding compounds, but also for the preparation 0! insulated electrical cables either by taping, extrusion, or other methods employed in the art. They also may be employed in the production of var- Although in the above examples I have shown copolymers of a, vinyl halide containing of the order oi 85 per cent'vinyl halide, I may use other 'copolymers in which the vinyl halide is present in lower concentrations, for example, from i to 70 per cent, by weight, or higher concentrations, for instance, as high as 98 per cent of the total weight of the copolymerizable materials. For maximum strength and flame-resisting prop erties, I prefer that the vinyl halide used in preparing the copolymer be present in the copolymer I in an amount equal to, by weight, at least to per cent, preferably 30 per cent, of the total weight of the copolymerizable ingredients.

It will be apparent that the compounds em ployed ,as stabilizers in my invention may also be used to stabilize other halogen-containing.

electrical stabilizer therefor comprising a compound having the general formula wherein R and R are each an alkyl radical, the former having from 3 to 10 carbon atoms and the latter having from 1 to 5 carbon atoms in the radical. A

2. A composition as in claim 1 wherein R is an alkyl radical having ten carbon atoms.

3. A composition comprising a polymeric mess including (1) polyvinyl chloride and, as a heat and light stabilizer therefor, (2) from 0.5 to ill percent, by weight, based on the weight of (1) of a compound having the same formula as set forth under (2). of claim 1.

'4. A composition comprising (1) the product of conjoint polymerization of a mixture containing a vinyl halide and a polymerizable vinyl ester of a lower saturated aliphatic monocarboxylic acid containing at most six carbon atoms and (2) from 0.5 to 10 per cent, by weight, based on the weight of (l) of a heat and light stabilizer therefor comprising a compound having the same formula as set forth under (2) of claim 1.

. 5. A composition as in claim 4 wherein vinyl ester isvinyl acetate.

6. A composition as in claim 4 wherein the vinyl halide is vinyl chloride.

the

"l. A composition comprising (1) a vinyl halide resin and (2) from 0.5 to 10 per cent, by weight, based on the weight of, (1) of a heat, light, and electrical stabilizer for (1) comprising a compound having the general formula where R is an alkyd radical containing from 3 to 10 carbon atoms.

8. A composition comprising (1) a copolymer obtained by the conjoint polymerization of a mixture comprising, by weight, a major portion of a vinyl halide and a minor portion of a vinyl ester 02 a lower saturated aliphatic monocarboxylic acid containing at most six carbon atoms, and (2) from 0.5 to 10 per cent, by weight, based on the weight of (1) of a compound represented by the formula n-o- -o-om Had-O-O 0 Pp HiiO--O Bil I under (2) of claim 9.

where R is an alkyl radical containing from 3 to v 10 carbon atoms.

9. A composition comprising (1) a copolymer obtained by conjoint polymerization of a mixture comprising, by weight, a major portion of vinyl chloride and a minor portion of vinyl acetate, and- (2) from 0.5 to 10 per cent, by weight, based onthe weight of (l) of a compound represented by the formula MOYER M. SAFFORD.

No references cited. f 

